KR20060132777A - Dispersion polycarbonate polyurethane resin - Google Patents

Abstract

Provided are a water dispersible polycarbonate polyurethane resin which is environmentally friendly, contains no organic solvent, and a method for preparing the polycarbonate polyurethane resin. The water dispersible polycarbonate polyurethane resin is represented by the formula. The method comprises the steps of heating polycarbonate diol and anionically functional diol at 100-120 deg.C to dissolve dimethyl butanoic acid in polycarbonate diol, removing moisture, injecting a diisocyanate compound, and injecting a neutralizer to prepare a prepolymer; dispersing the prepolymer in a dispersion device containing deionized water by force and injecting a chain extender to prepare a polycarbonate polyurethane; and filtering the polycarbonate polyurethane by using nonwoven or cotton cloth.

Description

Water Dispersible Polycarbonate Polyurethane Resin {DISPERSION POLYCARBONATE POLYURETHANE RESIN}

1 is a schematic diagram of a PUD pilot in one embodiment according to the present invention;

The present invention relates to an environment-friendly water-dispersible polycarbonate polyurethane resin having excellent physical and chemical properties, and more particularly, does not contain any organic solvents, and is a diisocyanate compound and a polyether / poly A polymerized composition obtained by polymerizing carbonate diol, which is a urethane resin having a solid content of about 40% by weight based on the total additive composition, and contains no traces of water-soluble solvents or organic solvents, and does not use a catalyst such as a metal catalyst. It is a friendly polyurethane resin. In the polyurethane additive composition according to the present invention, a polycarbonate diol or a polyether diol and a diol and a diisocyanate compound containing a carboxyl group to give a hydrophilic group when dispersed in water are added to a reaction tank, and the temperature is raised to 80-100 ° C. and stirred. After reacting for about 2-3 hours at 80-100 ℃, it is forcibly dispersed in water and subjected to amine-based long chain extension reaction. After completion of the reaction, the product was aged by aging at 30 ° C. for 12 hours to terminate the reaction.

Polyurethane is a polymer having excellent processability, coating property, elasticity and resilience, and is a resin applied in various technical fields such as impregnant, coating agent, adhesive, moisture-permeable waterproof agent and foam. However, organic solvents (DMF, DMAc, MEK, Acetone) and the like used in the manufacture of polyurethanes are harmful or harmful to humans or the environment and their use is restricted or regulated. Therefore, the development of water-dispersible PU is currently in progress, but it has been used in limited applications because it has a disadvantage in that physical properties, coating properties, elasticity, and rebound elasticity are inferior to solvent type PU.

It is manufactured by applying a small amount of organic solvents and water-soluble solvents (acetone, MEK, NMP) in the manufacturing process of polyurethane resin, and recovering the organic solvent after manufacturing the resin. And solvents), which can adversely affect the worker's environment during the work, and have factors that may damage the environment and the worker's environment in the manufacturing process.

 In addition, in general polyether / polyester / polycaprolactam TPU, there are disadvantages in that chemical resistance, heat resistance, friction resistance, stiffness, and weather resistance are poor, but in the case of polycarbonate polyurethane, chemical resistance, heat resistance, friction resistance, rigidity, weather resistance It is a very good polyurethane resin. However, such a polycarbonate polyurethane has a disadvantage in that it is difficult to manufacture a solvent-free type due to an increase in viscosity during the manufacturing process.

The present invention is to solve the problems of the prior art as described above, it is an object of the present invention to provide a polycarbonate polyurethane (PUD) and a method for producing the same excellent mechanical properties, imparting a solvent-free manufacturing process and products. .

The water-dispersed polycarbonate polyurethane resin according to the present invention is as follows.

Moreover, the manufacturing method of the water dispersion polycarbonate polyurethane resin by this invention,

The process of dissolving dimethylbutanoic acid (DMBA) in polycarbonate diol (PCD) by heating polycarbonate diol (PCD) and anion-imparting functional diol to 100 to 120 ℃, removing water, diisocyanate Polymerizing the prepolymer through a process of adding a system compound, a process of nitrogenizing the inside of the reactor, and a process of adding a neutralizing agent; Polymerizing the polycarbonate polyurethane (PUD) through a process of forcibly dispersing the prepolymer in a disperser including deionized water (DIW) and adding a chain extender; And filtering using a filter such as nonwoven fabric or cotton cloth.

The anion-imparting functional diol is any one or two selected from dimethylbutanoic acid (DMBA), dimethylpropane acid (DMPA), the diisocyanate compound is selected from MDI, IPDI, TDI, PPDI, HDI, H12MDI Any one or two or more, the neutralizing agent is any one or two or more selected from Diethylamine, Triethylamine, N-ethyldiamine, the chain extender is preferably any one or two or more selected from Ethylene diamine, 1-4cycllhexane diamine, Hydrize .

Polymerizing the prepolymer preferably has an NCO / OH molar ratio of 1.5 to 1.7.

The process of forcibly dispersing in the disperser containing the deionized water (DIW) is preferably within 1 hour.

In the process of adding the chain extender, the chain extender is preferably mixed with water so that the chain extender is 30 to 35 (weight)%.

Terms used in the present invention are as follows.

PTMEG: Polytetramethalene ether glycol

PPG: Polypropylene glycol

PCD: Polycabonate glycol

DMBA: Dimethylbutanoic acid

DMPA: Dimethylproponic acid

IPDI: Isoporon diisocyanate

TEA: Triethylamine

EDA: Ethylenediamine

MDI: 4,4-Diphenylmethane diisocyanate

TDI: Toluene diisocyanate

PPDI: p-Phenylene diisocyanate

HDI: 1,6-Hexamethylene diisocyanate

H12MDI: Cyclohexylmethane diisocyanate

DBA: Dibutylamine

IR: Infrared (FT / IR spectrometer)

The present invention will be described in detail through the following examples. However, these examples are for illustrative purposes only and the present invention is not limited thereto.

In the case of the polycarbonate polyol used in the present invention, C5, C5-C6 and C6 carbonate diols (PCD) and polyether polyols (PTMG) were prepared using a mixture or used alone. Since alkali resistance and friction resistance are very important when used for artificial leather or textile coating, yellowing may occur depending on external conditions when alkali resistance and heat resistance are used when general polyester is used, and its use is limited. In the case of polycarbonate polyol (PCD) of these polyols the molecular structure

HO- [R-OCO-] _n R-OH

-R-:-(CH2) ₂ -CH- (CH2) ₂ -or-(CH ₂ ) _9-

Mn600-3000 was used as the material having a molecular weight, and more specifically, 2000-3000 is preferably applied.

In the case of PTMG polyol,

HO [(CH ₂ ) ₄ -0] _n H

The molecular weight of Mn 650-2900 was used as the substance, and more specifically, 1000-2900 was selectively used. In the case of PPG, Mn1000-4000 was applied and optionally used.

Next, DMBA (Dimethyolbutanoic acid) and DMPA (Dimethyolproponic acid) were selectively used in the case of anion-imparting functional diol, and more specifically, DMPA was selectively used. The use of these anionic functional groups was used at a ratio of about 0.5-1.0 to the molar ratio of the entire polyol.

The neutralizing agent of the anionic functional group used in the present invention is Ammonia, Diethylamine, Triethylamine, Morpholine, N, N-Dimethylethanolamine, 2-Dimethylamino-2-methyl-1-propanol, Mono-isopropanolamine, Mono-ehthanolamine, N-Ethyldiamine, Triehtanolamine In particular, Diethylamine, Triethylamine, N-ethyldiamine and the like were selectively used.

In the case of the diisocyanate-based compound used in the present invention, MDI, TDI, IPDI, PPDI, HDI, H12MDI, and the like were selectively used, and more specifically, PPDI, IPDI, MDI, and the like were selectively used. In the case of the remaining diisocyanate, the reaction proceeds only by using an organic tin-based catalyst and is limited to its use. In the case of such diisocyanate compounds, an NCO / OH ratio was used at 1.5-1.7.

 As the chain extender used in the present invention, Hydrizine (Mn 32), Ethylenediamine (Mn 60), 1-4cyclohexane diamine (Mn 114), 2,4-Toleylenediamine (Mn 122.2), Isophorone diamine (Mn 170.3), Diethyltolune diamine ( Mn 178.0), 4,4-Methylene bis (2-chloro aniline) (Mn 267.2), etc. were used. Specifically, Ethylene diamine, 1-4cycllhexane diamine, and Hydrize were selectively used.

In the case of the UV / antioxidant used in the present invention, the Aryl phosphate-based antioxidant was used, and in the case of the UV absorber, a type having a non-functional group of the Benzoate / Sebacate series was used. In the case of a substance having a hydroxyl group, the reaction with NCO proceeded to limit its use.

The present invention is based on the above compounds in the case of the 1 l pilot polymerization reactor for the synthesis of water-dispersible polyurethane as described below and the 20 l scale dispersion device for water dispersion is not good dispersibility when using a general dispersion equipment homozeta Urethane dispersion equipment was produced separately.

In the case of Figure 1 is a schematic diagram of a two-batch synthesis equipment, the production of 100% polycarbonate (PUD) using a homo-zeta disperser in the reaction tank and an impeller of the preca method when manufacturing the prepolymer separately produced in one batch method It was.

The compounding table used in the polymerization process of the polymer of the present invention is shown in Table 1, and the polymerization process is as follows.

Table 1 Formulation Table of Polycarbonate Polyurethane

First, 4,000g (2M) of PCD (polycarbonate polyol Mw = 2,000), 149g (1.0M) of dimethylolbutanoic acid (DMBA), 13g (0.1%) of Triphenephosphate (TPP), and Tinuvin770 (sebaceate type 13g (0.1%)) were weighed. After stirring, it is heated to 120 ° C and stirred to remove moisture contained in polyols or other inputs, and when excess water is present, urea bonds occur, resulting in deterioration of product properties. After heating up to ℃, settle for about 20 ~ 30 minutes and cool down to 70 ℃, then add 955g (4.3M) of IPDI at elevated temperature of 70 ℃, and add IPDI at a time and input time is about 10 ~ 20 minutes. IPDI was added to maintain the temperature of the reactor at about 90-95 ° C. for about 2 hours and 30 minutes, and after the reaction for 2 hours and 30 minutes, the reactor temperature was lowered to about 90 ° C. or less and TEA 106g (1.05M) was added. Input over 10. When TEA is added above 90 ℃, TEA If it is released, it does not have sufficient neutralization, so it does not have good water dispersion, and neutralizes for 30 minutes after TEA is injected, and then it is forcibly dispersed in 6,500g of water in a water dispersion tank equipped with homozeta. The dispersing time is preferably within 30 minutes to 1 hour, preferably not more than 2 hours.If the temperature exceeds 60 ° C in the water dispersing tank, the urea reaction proceeds, so the temperature must be controlled. Forced agitation is continued for about 30 minutes after the prepolymer injection is completed, initially there is an increase in viscosity, but after a period of time, the viscosity is lowered, and the temperature is cooled to around 30 ° C. After 30 minutes of forced agitation, EDA 78g ( 1.3M) is diluted with 150g of water and chain extender, put into water dispersion tank for about 10 minutes, but do not exceed 40 ℃. After the reaction for 30 minutes, the temperature of the water dispersing tank is cooled below 30 ℃ and the reaction is terminated.

In the case of the physical properties of the product thus prepared is between NV 40 ~ 43%, pH 6 ~ 8, the appearance is a milky white emulsion.

Examples of blending products of polycarbonate and polyether type are as follows.

2,000 g polycarbonate polyol (PCD) (Mw = 2,000, 1 M), 2,000 g polyether polyol (PTMEG) (Mw = 2,000, 1 M), DMBA 178.8 g (Mw = 149, 1.2 M), TTP (Triphenylphosphate) 17 g, 17 g of Tinuvin770 is weighed and added to the reactor to raise the temperature to 120 ° C., and is allowed to stand for 30 minutes. After cooling to 70 ℃ to add 933.6g of IPDI to react for 2 hours 30 minutes at 90 ~ 95 ℃. At this time, the urethane reaction is an exothermic reaction, so pay attention to the temperature rise, and may cause discoloration of the product when reacted for more than 110 to 30 minutes. When the urethane reaction is finished, the reaction is neutralized with TEA 126.5g (5g excess) by cooling below 90 ° C, but the conditions are as described above. After the reaction proceeds for 30 minutes, if the pH is 7, the product is forcibly dispersed in a water dispersion tank using a homozeta type disperser in 6,300 g of water, and the conditions are as described above. After forced water dispersion, 60.1 g (1 M) of EDA is diluted in water and added thereto, but the conditions are performed under the above conditions. Physical properties of the final product are shown in <Table 2>.

Table 2 Property Values According to Examples

Application examples of the polycarbonate polyurethane (PCPU) thus prepared are as follows.

Preferred yarn is 75d / 25d (9 split) yarn and the mixing ratio is about 66.6% and Reg. The ratio of PET to modified PET, which is about to be weighted down, was compared with unpredicted fears by the daylight, friction, and washing experiments on fabrics that had undergone impregnation ⇒ alkali loss ⇒ dyeing. The result values for the Examples of each step are shown in Tables 3, 4, and 5, respectively.

Table 3 Alkali Reduction Example Result

<Table 4> Dyeing condition of alkali-reduced fabric

<Table 5> Daylight / Laundry / Friction Fastness Results

The present invention forcibly disperses the polymerized prepolymer in DIW (deionized water) using a disperser. In this case, the prepolymer should be dispersed within 1 hour from the first reactor to dispersion. If the time is delayed, the prepolymer may react with moisture in the air, resulting in poor water resistance and chemical resistance. In the case of the polycarbonate prepolymer, the viscosity of the polycarbonate is very high, and when dispersing, the rpm of the disperser is dispersed at 2500-3500 rpm. At this time, the temperature of the prepolymer should be maintained at 70-80 ℃. In addition, cooling should be carried out so that the temperature of the secondary reaction tank in which water is dispersed is kept below 35 ° C. The dispersion thus dispersed is stabilized by dispersion for about 30 minutes at high rotation, followed by a secondary reaction. In the second reaction, EDA is added to water (D / W) at a concentration of about 30-35% and divided for about 30 minutes. The disperser is continuously stirred in the course of dosing. At this time, the stirring speed is maintained at 1500-2000rpm. The temperature of the reaction tank in which the secondary reaction is performed should be maintained at 40 ° C. or lower, and after about 1 hour, the temperature of the reaction tank is cooled to room temperature (25-30 ° C.) or lower, and stirring of the disperser is stopped. After the packaging is left for more than 12 hours, the polymer is filtered by using a nonwoven fabric or cotton cloth to produce a polymerized material. In addition, referring to <Table 1> for the production of polycarbonate polyurethane (PCU) to prepare a product.

When seaweed and split yarn fabrics are impregnated with polycarbonate polyurethane (PCPU) according to the present invention to reduce alkali, or dyeing, or after dyeing to reduce alkali by impregnating / padding polycarbonate polyurethane after the dyeing, Formation of a thin film shows that about 0.5 ~ 1 level of color fastness increases in the test of color fastness, daylight and washing fastness.

In addition, in the case of the top coat of the transfer paper, one-component urethane is used, and a product having excellent mechanical properties is generally used in view of surface protection. In addition, in the case of general one-component urethane, the hardness is high and the protection is used, but in the case of polycarbonate, the hardness, such as polyurethane of general polyether and ester, is excellent in mechanical properties, and thus the wear resistance, impact resistance, and heat resistance are excellent. It is 1 ~ 2 times stronger, and it has the property of almost twice the protection with the same thickness of film and can solve the problem of existing products.

In the case of the transfer and surface coating, one-component polyurethane is used, and when the transfer is performed by using a transfer paper, a disadvantage occurs in that the pattern is blurred due to the characteristics of the soft urethane. This is the case that the polyol of the linear polyol due to the heat transfer of the dye occurs a disadvantage that the pattern is blurred. However, when coating polycarbonate urethane alone or blended products, migration by heat does not occur, so that the blurring of the pattern and abrasion resistance may be improved. As in the case of the top coat of the transfer paper, the polycarbonate polyol has a characteristic in that dyes do not freely move due to the carbonate group, and according to such a structure, a high density is formed due to a good lamination in the polyurethane structure. Same as This is the same principle as the phenomenon in which the branch type shows a higher density polyethylene in the same shape as the linear structure and the branch structure in the case of polyester.

As described above, according to the present invention, the mechanical properties are excellent, there is no adverse effect on the operator's environment during work by imparting solvent-free manufacturing process and product, there is no effect of environmental pollution and factors that harm the worker's environment in the manufacturing process. There is.

In addition, depending on the application can be solved by applying a conventional polycarbonate polyurethane resin, environmentally friendly products can be obtained from these applications.

Claims (6)

A water-dispersible polycarbonate polyurethane resin having a structure represented by the following formula.

In the manufacturing method of water-dispersible polycarbonate polyurethane resin, The process of dissolving dimethylbutanoic acid (DMBA) in polycarbonate diol (PCD) by heating polycarbonate diol (PCD) and anion-imparting functional diol to 100 to 120 ℃, removing water, diisocyanate Polymerizing the prepolymer through a process of adding a system compound, a process of nitrogenizing the inside of the reactor, and a process of adding a neutralizing agent; Polymerizing the polycarbonate polyurethane (PUD) through a process of forcibly dispersing the prepolymer in a disperser including deionized water (DIW) and adding a chain extender; Method of filtering using a filter such as nonwoven fabric or cotton cloth; Water-dispersible polycarbonate polyurethane resin manufacturing method comprising a. The method of claim 2, The anion-imparting functional diol is any one or two selected from dimethylbutanoic acid (DMBA), dimethylpropane acid (DMPA), The diisocyanate compound is any one or two or more selected from MDI, IPDI, TDI, PPDI, HDI, H12MDI, The neutralizing agent is any one or two or more selected from Diethylamine, Triethylamine, N-ethyldiamine, The chain extending agent is any one or two or more selected from Ethylene diamine, 1-4cycllhexane diamine, Hydrize manufacturing method of water-dispersible polycarbonate polyurethane resin. The method according to claim 2 or 3, Polymerizing the prepolymer is a method for producing a water-dispersible polycarbonate polyurethane resin, characterized in that the NCO / OH ratio is 1.5 to 1.7. The method of claim 4, wherein The process of forcibly dispersing in the disperser containing the deionized water (DIW) is water dispersion polycarbonate polyurethane resin manufacturing method, characterized in that within 1 hour. The method of claim 5, The process of injecting the chain extender is a water dispersion polycarbonate polyurethane resin production method, characterized in that the mixture is added to the water so that the chain extender 30 to 35 (weight)%.

Images